Gasoline composition

ABSTRACT

A gasoline composition comprising (a) gasoline, (b) a deposit inhibitor or a detergent containing a basic nitrogen atom, (c) a carrier oil, and (d) one or more compounds selected from the group consisting of an ester of a fatty acid and an alkylene oxide addition compound to bisphenol, a compound obtained by the ester exchange reaction of an alcohol and a triglyceride-type fat or oil, an aliphatic or aromatic carboxylic acid, a metal salt of an aliphatic or aromatic carboxylic acid, an ester of an aliphatic or aromatic carboxylic acid and an alcohol, and an ester of boric acid. The composition has superior heat resistance and is excellent in removing deposits in the fuel intake systems and in keeping the systems clean.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a gasoline composition exhibiting anexcellent detergent effects on the fuel intake system.

2. Description of the Background Art

Deposits and sludges produced in the fuel system and the combustionchamber of internal combustion engines are known to decrease thefunctions of the engines and also to have an adverse effect on exhaustgas. Deposits produced in intake valves and intake ports reduce outputpower of the engine, decrease driving performances, and increase theamount of exhaust gases. Performances of engines are being more and morepromoted in recent years, and these high performance engines are moresensitive to these deposits.

Deposits in intake valves, in particular, cause serious problems inelectronic controlled fuel injection systems, of which the use isrecently increasing in passenger cars. Although these systems, whichstrictly control the fuel-air mixture, not only promote the engineperformances but also are effective for energy saving and exhaust gascontrol, this fuel-air mixture control system ceases to correctlyfunction if gasoline injected from the injection system comes intocontact with deposits attached to the intake valves. The resultingmalfunction of the fuel-air mixture control system seriously affects thedrivability of the automobile.

Various gasoline additives are added to gasoline in order to preventaccumulation of deposits in fuel intake systems, such as carburetors andintake valves, to remove deposits therefrom, and to clean combustionchambers.

Compositions comprising a detergent, which is an oil-soluble activecomponent containing a basic nitrogen such as amino group or amidegroup, and a carrier oil, which is typically a mineral or synthetic oil,are conventionally known as gasoline additive compositions. Thedetergent acts on soils and dirts which may deposit on the intake systemto keep this system clean. The carrier oil is used to keep the detergentactive. High boiling-point and high viscosity oils having excellent heatstability are usually used as a carrier oil. These oils have a functionof a dispersing agent, by which the detergent is kept active. They alsohave a function of protecting metal surfaces in the intake system byforming liquid films. Polyolefins, polyoxyalkylenes (Japanese PatentPublication (kokoku) No. 48556/1981), esters, and the like are known assynthetic oils used as the carrier oil.

In order to adapt to engines of which the performances are more and morepromoted in recent years, a high level of detergency is required forintake systems, particularly for intake valves. In particular, in orderto enable the detergent to exhibit its actions more effectively, thecarrier oil must be sufficiently heat resistant (intake valves are at200°-300° C.), must have good compatibility with the detergent, and mustwell dissolve soils and dirts (oxidated or deteriorated matters fromfuels and engine oils) in the intake system.

With the object of satisfying these requirements, some fuels andgasoline additives have been proposed, including (1) a fuel for internalcombustion engines, in which two different types of compounds are usedas carrier oils (Japanese Patent Application Laid-open (kokai)173194/1990); (2) a fuel additive composition comprising a polyetheramine-type compound (U.S. Pat. No. 5,018,029); and (3) a fuel additivecomposition comprising a polyether compound and a compound having anamine-type nitrogen atom and an oxyalkylene group or a polyamine(Japanese Patent Application Laid-open (kokai) 114089/1992).

These gasoline additives and gasoline compositions are not satisfactoryin their detergent effects.

Development of a gasoline composition having a further improveddetergent effect has therefore been desired.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide a gasolinecomposition comprising,

(a) gasoline,

(b) 1-10,000 ppm of a deposit inhibitor or a detergent containing abasic nitrogen atom,

(c) 1-10,000 ppm of a carrier oil, and

(d) one or more heat resistance improvers selected from the groupconsisting of,

(d-1) an ester of a fatty acid and an alkylene oxide addition compound,wherein the compound to which the alkylene oxide is added has thefollowing formula (1), ##STR1## wherein X represents ##STR2## (whereinZ¹ and Z² are individually a hydrogen atom, a trifluoromethyl group, ora substituted or unsubstituted alkyl or alkenyl group having 1-6 carbonatoms, or a phenyl group), and Y¹ and Y² are individually a hydrogenatom or a substituted or unsubstituted alkyl or alkenyl group having 1-6carbon atoms, or a phenyl group,

(d-2) a compound obtained by the ester exchange reaction of an alcoholand a triglyceride-type fat or oil or an alkylene oxide adduct thereof,

(d-3) an aliphatic or aromatic carboxylic acid having 12-30 carbonatoms,

(d-4) a metal salt of an aliphatic or aromatic carboxylic acid having4-30 carbon atoms,

(d-5) an ester of an aliphatic or aromatic carboxylic acid having 12-30carbon atoms and an alcohol having 1-8 carbon atoms, and

(d-6) an ester of boric acid.

The gasoline composition of the present invention exhibits more improvedheat resistance and a better detergent effect than conventionalcompositions containing the above-described components (a), (b), and(c). In particular, it has remarkably improved deposit removingproperties from the gasoline engine intake systems and greatly promoteddetergent capability which lasts over a long period of time.

Other and further objects, features and advantages of the presentinvention will be more fully evident from the following description.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

There are no specific limitations to the gasoline which is used ascomponent (a) in the composition of the present invention, so long asthe gasoline is that for use in spark-ignition engines, such asautomobile gasoline and aircraft gasoline. Reformed gasoline, low-leadedgasoline, clear gasoline, and the like are included.

The compound containing a basic nitrogen atom, component (b), is addedto the composition of the present invention as a deposit inhibitor or adetergent. Any compounds containing a basic nitrogen atom which arecommonly used as a detergent for fuel intake systems can be used ascomponent (b) without any specific limitations. Polyether amine-typecompounds, long-chain alkylamine compounds, long-chain alkenylaminecompounds, benzylamine compounds, and succinimide compounds are given asexamples. Among these, polyether amine-type compounds, long-chainalkylamine compounds, and long-chain alkenylamine compounds arepreferred, with particularly preferred being polyether amine-typecompounds.

Compounds represented by the following formula (2) can be given asspecific polyether amine-type compounds.

    R.sup.1 --O(A.sup.1 O).sub.n --A.sup.2 --X.sup.1           (2)

wherein R¹ represents an alkyl or alkylphenyl group having 1-50 carbonatoms, A¹ O is an alkylene oxy group having 2-6 carbon atoms, A² is agroup, ##STR3## (wherein Y³ and Y⁴ individually represent a hydrogenatom, or a methyl, ethyl or carboxy group, and 1 is an integer of 3-5),and X¹ represents a group, ##STR4## (wherein Zs may be the same ordifferent and individually represent a hydrogen atom, a hydrocarbylgroup having 1-10 carbon atoms, or a hydrocarbonyl group having 2-10carbon atoms; Z³ s may be the same or different and individuallyrepresent and alkylene group having 2-6 carbon atoms, which may besubstituted by a hydroxy group; Z⁴ represents a carbonyl, alkylenecarbonyl, or alkylene group which has an adjacent bonding and 2-4 carbonatoms; e is 0 or 1, preferably 1; f is 0-4, preferably 0-2; g is 0 or 1,preferably 0; h is 0 or 1, preferably 0; i is 0 or 1, preferably 1; j is0 or 1, provided that j must be 1 when g is 0; and n is an integer of1-50).

There are no specific limitation to the structure of alkylene oxidegroup, A¹ O, in formula (2) of the compound. Any alkylene oxide groupswith an optional structure, including those added by an isomer mixturethereof, can be used.

Among these, the compounds of the following formula (2-a) described inU.S. Pat. No. 5,089,029 are especially preferred.

    R.sup.1 --O--(A.sup.1 O).sub.n --(C.sub.3 H.sub.6 NH).sub.m H(2-a)

wherein m is an integer of 1-3, and R¹, A¹, and n are the same asdefined above. Among the compounds of formula (2-a), those having R¹containing 10-50 carbon atoms and A¹ containing 2-4 carbon atoms areparticularly preferred. U.S. Pat. No. 5,089,029 is herein incorporatedby reference.

As the long-chain alkylamines or the long-chain alkenylamines, compoundsof the following formula (3) can be given.

    R.sup.2 --(NHCH.sub.2 CH.sub.2).sub.d --NH--X.sup.2        (3)

wherein R² represents a long-chain alkyl or alkenyl group having amolecular weight of at least 700, X² represents a hydrogen atom or along-chain alkyl or alkenyl group having a molecular weight of at least700, and "d" denotes an integer of 0-5.

Polyolefin residues, such as polyethylene, polypropylene, andpolybutene, are given as the long-chain alkyl or alkenyl groups for R²or X² in formula (3). Compounds having an integer of 1-5 for "d" arepreferred.

A typical example of the compound represented by formula (3) can beprepared by chlorinating a polyolefin and reacting the chlorinatedpolyolefin with a polyamine.

The amount of component (b) to be incorporated for providing gooddeposit inhibition or detergent effects to the composition of thepresent invention is 1-10,000 ppm, preferably 10-1,000 ppm.

As the carrier oil of component (c), an alkylene oxide adduct to analcohol or an alkylphenol having 10-50 carbon atoms, as a majorcomponent, is preferred, even though mineral oils and synthetic oils arewell acceptable.

Given as the alcohol having 10-50 carbon atoms are various naturalsaturated or unsaturated alcohols, linear monohydric alcohols producedby the Ziegler method, and branched alcohols obtained by the oxoreaction or the Guerbet reaction. Specific examples of these alcoholsinclude natural alcohols, such as decyl alcohol, lauryl alcohol,palmityl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol,oleyl alcohol, elaisyl alcohol, and erca alcohol; linear monohydricalcohols having 10-30 carbon atoms produced by the Ziegler method;branched alcohols having 10-24 carbon atoms produced by the oxoreaction; and branched alcohols having 16-24 carbon atoms produced bythe Guerbet reaction.

As alkylphenols having 10-50 carbon atoms, those having one or two alkylgroups having 4-40 carbon atoms, particularly 4-30 carbon atoms arepreferred. Specific examples which can be preferably used arebutylphenol, amylphenol, octylphenol, nonylphenol, dinonylphenol,dodecylphenol, cumylphenol, alkylphenols having C₁₈ -C₂₄ alkyl groups,and alkylphenols obtained by reacting a C₆ -C₃₀ α-olefin and phenol.

As the alkylene oxide added to these alcohols or alkylphenols, thosehaving 2-6, especially 3-4, carbon atoms, are preferred. There are nospecific limitation to the structure of the alkylene oxide. Any isomersor mixtures thereof can be used. The number of mols of the alkyleneoxides added is preferably 10 or more. If the number of mols of alkyleneoxides added is smaller than 10, the detergency effects at the intakevalve are poor. Although the upper limit of the number of mols is notspecifically limited, the products with more than 50 mols of alkyleneoxides added are difficult to manufacture, and are thus uneconomical.

These alkylene oxides may be added to the above-mentioned alcohols oralkyl phenols by a conventional method. For example, the alkylene oxidemay be reacted by adding it either in a liquid or gaseous state to thealcohol in the presence of sodium hydroxide while heating and optionallyusing a suitable solvent. The random addition polymerization, in which amixture of two or more kinds of alkylene oxides are reacted, and theblock addition polymerization, which consists of successive reactions ofdifferent kinds of alkylene oxides, are also applicable.

Esterified or etherified compounds of the alkylene oxide adduct toalcohol or alkyl phenol may also be used as the component (c). Theesterified compounds include esters of C₁ -C₂₀ fatty acids among theabove-mentioned fatty acids, and the etherified compounds include ethersof C₁ -C₂₁ alcohols, for example, alcohols having 20 or smaller carbonatoms among the above-mentioned alcohols, such as methanol, ethanol,propanol, or butanol.

The amount of component (c) to be incorporated for providing excellentdetergent effects to the composition of the present invention is1-10,000 ppm, preferably 10-1,000 ppm.

The component (d) of the composition of the present invention isparticularly useful for improving heat resistance. The addition of thiscomponent, however, increases not only the heat resistance, but also thedetergency effect and the long-lasting effect of the detergentcapability.

Component (d-1) is an ester of a fatty acid and an alkylene oxide adductof the compound represented by the formula (1). In formula (1), includedin the substituted or unsubstituted alkyl or alkenyl group having 1-6carbon atoms for Z¹, Z², Y¹, and Y² are alkyl groups, alkenyl groups,hydroxyl-substituted alkyl groups, and hydrocarbyl-substituted alkylgroups. Of these, unsubstituted alkyl or alkenyl groups, particularlyunsubstituted alkyl groups, are preferred. Given as examples of C₁ -C₆alkyl groups which can be preferably used include methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,n-pentyl, and n-hexyl groups.

Specific examples of the compound of formula (1) are bisphenol A,bisphenol F, bisphenol C, bisphenol E, bisphenol Z, bisphenol S,bisphenol AF, bisphenol AP, diisopropyl-bisphenol A,1,1-ethylidene-bisphenol, methyl-ethyl-methylene-bisphenol,methyl-isobutyl-methylene-bisphenol, methyl-hexyl-methylene-bisphenol,methyl-phenyl-methylene-bisphenol, and 4,4-thiodiphenol.

As the alkylene oxide to be added to the compound of formula (1), thosehaving 2-6 carbon atoms, especially 2-4 carbon atoms, are preferred.Specific examples of the alkylene oxide include ethylene oxide,propylene oxide, and butylene oxide. The average number of mols of thealkylene oxide to be added is 1-30, and preferably 1-5 mols. If thisnumber of mols exceeds 30, the addition compound obtained is too viscousto be adequately fluid.

Fatty acids having 1-30 carbon atoms, preferably 5-20 carbon atoms, areused for forming esters with these alkylene oxide addition compounds.Specific fatty acids include acetic acid, propionic acid, n-butanoicacid, iso-butanoic acid, n-pentanoic acid, iso-pentanoic acid,n-hexanoic acid, 2-ethylbutanoic acid, cyclohexanoic acid, n-heptanoicacid, iso-heptanoic acid, methylhexanoic acid, n-octanoic acid,dimethylhexanoic acid, 2-ethylhexanoic acid, 2,4,4-trimethylpentanoicacid, iso-octanoic acid, 2,5,5-trimethylhexanoic acid, n-nonanoic acid,iso-nonanoic acid, iso-decanoic acid, iso-undecanoic acid,2-butyloctanoic acid, dodecanoic acid (lauric acid), tridecanoic acid,tetradecanoic acid, hexadecanoic acid, and octadecanoic acid.

The addition reaction of the compound of formula (1) and the alkyleneoxide, and the reaction of the thus-obtained alkylene oxide additioncompound and the fatty acid can be carried out by conventional methods.The conversion rate of the resulting ester, which is component (d-1), ispreferably 50-100% based on the hydroxy groups of the alkylene oxideaddition compound.

Component (d-2) used in the present invention is a compound obtained bythe ester exchange reaction of an alcohol and a triglyceride-type fat oroil or an alkylene oxide adduct thereof. Vegetable oils, such as coconutoil, palm oil, and soybean oil; animal oils, such as tallow oil andwhale oil; and fish oils, are given as examples of the triglyceride-typefat or oil. They may be used either singly or in combination of two ormore.

These triglyceride-type fats or oils may be used after addition ofalkylene oxides. Alkylene oxides having 2-6, particularly 2-4, carbonatoms can be preferably used for this purpose. There are no specificlimitations to the structure of such alkylene oxides. Any isomers ormixtures of alkylene oxides can be used. The number of mols of alkyleneoxides to be added is preferably 2-30. If this number of mols exceeds30, the resulting addition compound has a high viscosity and is lessfluid.

Either monohydric or polyhydric alcohols may be used as the alcohol forthe ester exchange reaction. Linear or branched alcohols are given asexamples of monohydric alcohols. These alcohols specifically includepropanol, butanol, pentanol, hexanol, octanol, decyl alcohol, laurylalcohol, palmityl alcohol, stearyl alcohol, eicosyl alcohol, behenylalcohol, oleyl alcohol, elaisyl alcohol, and erca alcohol. Given asexamples of polyhydric alcohols are glycerine, trimethylolpropane,pentaerythritol, mesoerythritol, sorbitol, ethylene glycol, andpropylene glycol.

Among these alcohols, those having a molecular weight of 200 or smallerare particularly preferred.

The ester exchange reaction can be carried out by a conventional method,for example, a triglyceride-type oil or fat, or an alkylene oxide addedcompound thereof, is reacted with an alcohol under heating in thepresence of a catalyst such as anhydrous potassium carbonate using, ifnecessary, a suitable solvent. The molar ratio of the triglyceride-typeoil or fat, or the alkylene oxide added compound thereof, and thealcohol is preferably 1:0.1-1:5, and particularly preferably 1:0.5-1:2.

These compounds for the component (d-2) is preferable in view of theavailability at a low cost, the excellent biodegradable characteristics,and the minimal risks of causing environmental pollution.

Given as examples of the carboxylic acid for component (d-3) aresaturated fatty acids, such as lauric acid, myristic acid, stearic acid,palmitic acid, alkylmalonic acid, and alkylsuccinic acid; unsaturatedfatty acids, such as oleic acid, linoleic acid, and linolenic acid;aromatic carboxylic acids, such as alkylsalicylic acid. Beside thesecarboxylic acid compounds, fatty acid mixtures of animal or vegetableorigin which contain these carboxylic acids, such as soybean fatty acid,rapeseed fatty acid, tallow oil fatty acid, and castor oil fatty acid,can also be used.

As examples of the carboxylic acid for the metal salt of carboxylic acidfor component (d-4), alkylmalonic acid, alkylsuccinic acid,alkenylsuccinic acid, and alkylsalicylic acid can be given. As the saltsof the carboxylic acid, salts of alkali metal, such as lithium, sodium,and potassium; and salts of alkaline earth metal, such as barium,calcium, and strontium, can be given.

The same carboxylic acids used as component (d-3) can be used as thecarboxylic acid for forming the ester of component (d-5). Given asexamples of the alcohol for forming the esters are monohydric alcohols,such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol,and amyl alcohol; and polyhydric alcohols such as glycerine. Typicalexamples of the ester derived from these carboxylic acids and alcoholsare methyl ester of tallow oil, butyl ester of tallow oil, butylstearate, diethyl alkylmalonate, methyl ester of castor oil, methylalkyl(C₁₆)salicylate, glycerol mono-oleate, and the like.

Borates containing or not containing nitrogen can be used as component(d-6). More particularly, products obtained by the reaction of boricacid and an alcohol selected from monohydric alcohols, polyhydricalcohols, partial esters of polyhydric alcohol, monoalkanol amines,dialkanol amines, and trialkanol amines can be given as the component(d-6).

Among these, the products obtained by the dehydration reaction of anamine containing hydroxy group and boric acid can be given asnitrogen-containing borates. Specific examples are the reaction productsof boric acid and an amine compound represented by the following formula(4), ##STR5## wherein R³ is a hydrogen atom or an alkyl group having1-20 carbon atoms, and R⁴ and R⁵, which may be the same or different,represent a group, ##STR6## (wherein R⁶ is a hydrogen atom or a methylgroup, and 1 is a number of 1-10) or an alkyl group having 1-20 carbonatoms, provided that both R⁴ and R⁵ are not alkyl groups at the sametime.

Included in the amine compounds of the above formula (4) are alkanolamines, such as ethanolamine and isopropanolamine; N-alkyldiethanolamines such as N-butyldiethanolamine; and N-alkylisopropanolamines. The following compounds are given as typical examplesof the borates obtained by the reaction of N-butyldiethanolamine andboric acid at the amine and boric acid molar ratio of 2:1. ##STR7##

Further, given as examples of borates not containing nitrogen arereaction products of boric acid and a monohydric alcohol, a polyhydricalcohol, or a partial ester of polyhydric alcohol, for example,(poly)alkylene glycol borates, such as glycerol borate stearate,glycerol borate oleate, triethylene glycol monomethyl ether triborate,and polyoxyethylene glycerol borate stearate.

These components (d-1) to (d-6) may be used either individually or incombination of two or more.

Among components (d-1) to (d-6), (d-1) is particularly preferred forproviding the gasoline composition with not only heat resistance butalso detergency and a long-lasting effect of the detergency. Component(d-2) is preferred due to its biodegradable properties. Due to thesecharacteristics possessed by components (d-1) and (d-2) their combineduse is also preferred.

The amount of component (d) to be incorporated for providing excellentheat resistance, detergency, and long-lasting effect of the detergencyto the composition of the present invention is 1-5,000 ppm, preferably3-500 ppm.

The ratio by weight of components (b) to (d) in the gasoline compositionof the present invention is (b):(d)=99.5:0.5 to 70:30, particularlypreferably 99:1 to 80:20. The ratio by weight of components (b) to (c)is (b):(c)=5:95 to 95:5, particularly preferably 40:60 to 90:10.Further, the ratio by weight of components (b)+(c) to component (d) is99.5:0.5 to 70:30, preferably 99:1:to 80:20, and particularly preferably98:2 to 90:10.

The total amount of components (b), (c) and (d) in the gasolinecomposition of the present invention is 3-25,000 ppm, and preferably5-20,000 ppm, and particularly preferably 10-15,000 ppm.

There are no specific limitation to the method of the addition ofcomponents (b) to (d). It is possible to prepare a mixture of two ormore of the components (b), (c) and (d) in advance and to add thismixture to component (a), or to add the components (b), (c) and (d)separately to component (a). Only incorporation of these components ingasoline in whatever manner is required.

Beside the above-described essential components, any additives, such asrust preventives, anti-emulsion agents, antioxidants, and metaldeactivators, may be added to the gasoline composition of the presentinvention.

Japanese Patent Application No. 95926/1993 filed on Apr. 22, 1993,Japanese Patent Application No. 109459/1993 filed on May 11, 1993,Japanese Patent Application No. 246897/1993 filed on Oct. 1, 1993,Japanese Patent Application No. 256009/1993 filed on Oct. 13, 1993,Japanese Patent Application No. 323960/1993 filed on Dec. 22, 1993,Japanese Patent Application No. 323961/1993 filed on Dec. 22, 1993,Japanese Patent Application No. 323692/1993 filed on Dec. 22, 1993, andJapanese Patent Application No. 323693/1993 filed on Dec. 22, 1993 areherein incorporated by references.

Other features of the invention will become apparent in the followingdescription of the exemplary embodiment which is given for illustrationof the invention and is not intended to be limiting thereof.

EXAMPLES Example 1

A test engine was driven in the test mode described below using thegasoline additive compositions of the formulation shown in Tables 1-4.The amounts of deposits were measured after the drive.

Gasoline which produces deposits in an amount of 1305 mg or 1310 mg pervalve in this test was used as the fuel. The gasoline additivecompositions were added to this gasoline in the amounts shown in Tables1-4. The results are given in Tables 1-4.

Test engine: Toyota 1G-EU engine (trademark, manufactured by ToyotaMotor Corp., 2000 cc)

Test mode: One cycle

    ______________________________________                                        Idling             30     seconds                                             1300 rpm           60     seconds                                             1850 rpm           120    seconds                                             3000 rpm           60     seconds                                             ______________________________________                                    

Test hour: 120 hours (1600 cycles)

The following compounds were used for preparing the compositions for thetest.

A-1: Lauric acid diester of ethylene oxide adduct (2 mols) to bisphenolA

A-2: 2,5,5-Trimethylhexanoic acid diester of propylene oxide adduct (10mols) to bisphenol A

A-3: n-Octanoic acid diester of butylene oxide adduct (5 mols) tobisphenol A

A-4: An ester exchange reaction product obtained by the reaction ofcoconut oil and butanol (molar ratio=1:2) at 200° C. with the additionof anhydrous potassium carbonate

A-5: A product obtained in the same manner as A-4 from (i) an ethyleneoxide (10 mol) adduct to palm oil and (ii) glycerine (molar ratio,(i):(ii)=1:0.8)

A-6: A product obtained in the same manner as A-4 from (i) a propyleneoxide (5 mol) adduct to soybean oil and (ii) trimethylol propane (molarratio, (i):(ii)=1:0.5)

A-7: Stearic acid

A-8: Oleic acid

A-9: Glycerol mono-oleate

A-10: Butyl stearate

A-11: Potassium salt of methyl alkyl(C₁₆) salicylate

A-12: Sodium isobutenyl succinate

A-13: A reaction product of polyoxyethylene alkyl amine (Amiet 102:trademark, manufactured by Kao Corp.) and boric acid (molar ratio 1:1)

A-14: A reaction product of N-butyldiethanolamine and boric acid (molarratio 2:1)

A-15: Glycerol borate oleate (Emulbone S-80: trademark, manufactured byToho Chemical Co., Ltd.)

A-16: Polyoxyethylene glycerol borate palmitate (Emulbone T-40:trademark, manufactured by Toho Chemical Co., Ltd.)

B-1: ##STR8## (wherein R^(1') is a polyisobutenyl group having amolecular weight of 900)

B-2: R^(3') --NH--CH₂ CH₂ --NH₂ (wherein R^(3') is a polyisobutenylgroup having a molecular weight of 800)

B-3: ##STR9## (wherein R^(4') is a polyisobutenyl group having amolecular weight of 800)

B-4: ##STR10## (wherein BO represents 1,2-butylene oxy group) B-5:##STR11## (wherein BO represents an alkylene oxy group consisting of1,2-isomer, 2,3-isomer and iso-isomer of butylene oxide)

B-6: ##STR12## (wherein PO represents propylene oxy group) C-1:1,2-Butylene oxide (17 mols) adduct to nonyl phenol

C-2: Propylene oxide (20 mols) adduct to dodecyl phenol

C-3: Butylene oxide (a mixture of 1,2-isomer, 2,3-isomer and iso-isomer;15 mols) adduct to nonyl phenol

C-4: Propylene oxide (20 mols) adduct to nonyl phenol

                  TABLE 1                                                         ______________________________________                                                    Amount      Deposit at intake valve                               Component   (ppm)       (mg/valve)                                            ______________________________________                                        None        --          1305                                                  A-1         200         850                                                   A-2         200         785                                                   A-3         200         812                                                   B-1         200         1507                                                  B-2         200         1378                                                  B-3         200         1246                                                  B-4         200         1120                                                  B-5         200         1246                                                  B-6         200         1263                                                  B-1/A-1     100/100     512                                                   B-2/A-2     100/100     479                                                   B-1/C-1     100/100     872                                                   B-2/C-2     100/100     1113                                                  B-3/C-1     100/100     1321                                                  B-4/C-2     100/100     868                                                   B-5/A-3     100/100     912                                                   B-6/A-2     100/100     948                                                   B-1/A-1/C-1 80/60/60    312                                                   B-2/A-2/C-2 80/60/60    253                                                   B-3/A-3/C-1 80/60/60    183                                                   B-4/A-2/C-1 80/60/60    112                                                   B-5/A-1/C-1 20/100/80   231                                                   B-6/A-2/C-2 20/100/80   210                                                   B-1/B-3/A-1/C-1                                                                           30/50/80/40 304                                                   B-2/B-5/A-1/C-2                                                                           40/40/100/20                                                                              217                                                   B-6/A-1/C-4 95/10/95    81                                                    B-5/A-2/C-1  80/20/100  103                                                   B-4/A-3/C-3  80/20/100  107                                                   ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                                    Amount      Deposit at intake valve                               Component   (ppm)       (mg/valve)                                            ______________________________________                                        None        --          1310                                                  A-4         200         925                                                   A-5         200         989                                                   A-6         200         1003                                                  A-4/B-1     100/100     621                                                   A-5/B-2     100/100     587                                                   A-6/B-3     100/100     476                                                   A-4/B-4     100/100     721                                                   A-5/B-5     100/100     613                                                   A-6/B-6     100/100     644                                                   A-4/C-1     100/100     721                                                   A-5/C-2     120/80      651                                                   A-6/C-3     100/100     593                                                   A-4/C-4     120/80      635                                                   A-4/B-4/C-1 80/60/60    260                                                   A-5/B-1/C-2 80/60/60    309                                                   A-6/B-2/C-3 80/60/60    249                                                   A-4/B-3/B-4/C-4                                                                           80/30/30/60 347                                                   A-4/B-2/B-6/C-4                                                                           70/20/30/80 244                                                   A-4/B-6/C-4 10/95/95    115                                                   A-5/B-5/C-1  80/20/100  130                                                   ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                                      Amount    Deposit at intake valve                               Component     (ppm)     (mg/valve)                                            ______________________________________                                        None          --        1305                                                  A-7           200       1344                                                  A-8           200       1721                                                  A-9           200       1467                                                  B-1           200       1507                                                  B-2           200       1378                                                  B-3           200       1246                                                  B-4           200       1199                                                  B-5           200       1287                                                  B-6           200       1413                                                  C-1           200       1320                                                  C-2           200       1513                                                  C-3           200       1621                                                  C-4           200       1407                                                  A-7/C-1       100/100   1260                                                  A-8/C-4       100/100   1196                                                  B-1/C-1       100/100   1021                                                  B-2/C-2       100/100   1113                                                  A-7/B-1       100/100   872                                                   A-7/B-1/C-1   4/76/120  242                                                   A-8/B-2/C-2   4/76/120  381                                                   A-7/A-3/B-3/C-1                                                                             2/2/76/120                                                                              421                                                   A-8/A-4/B-4/C-1                                                                             2/2/76/120                                                                              473                                                   A-11/B-1/C-2  4/120/76  360                                                   A-12/B-2/C-2  4/120/76  405                                                   A-7/B-1/B-5/C-1                                                                             4/70/50/76                                                                              378                                                   A-8/B-3/B-6/C-2                                                                             4/70/50/76                                                                              366                                                   A-7/B-6/C-4   4/76/120  136                                                   A-8/B-5/C-1   4/76/120  140                                                   A-11/B-4/C-3  4/76/120  139                                                   ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                    Amount      Deposit at intake valve                               Component   (ppm)       (mg/valve)                                            ______________________________________                                        None        --          1305                                                  A-13        200         1482                                                  A-14        200         1421                                                  A-15        200         1530                                                  A-16        200         1515                                                  B-1         200         1507                                                  B-2         200         1378                                                  B-3         200         1246                                                  B-4         200         1414                                                  B-5         200         1119                                                  B-6         200         1237                                                  A-13/C-1    100/100     1216                                                  A-14/C-3    100/100     1334                                                  B-1/C-1     100/100     1005                                                  B-2/C-2     100/100     1113                                                  B-3/C-4     100/100     989                                                   B-4/C-1     100/100     1003                                                  A-13/B-1    100/100     872                                                   A-13/B-1/C-1                                                                              4/76/120    546                                                   A-14/B-3/C-2                                                                              4/76/120    491                                                   A-15/B-4/C-1                                                                              4/76/120    415                                                   A-16/B-2/C-1                                                                              4/76/120    483                                                   A-13/B-2/B-5/C-2                                                                          40/20/20/120                                                                              734                                                   A-14/B-3/B-6/C-3                                                                          40/20/20/120                                                                              813                                                   A-13/B-6/C-4                                                                              4/76/120    137                                                   A-14/B-5/C-1                                                                              4/76/120    145                                                   A-15/B-4/C-3                                                                              4/76/120    141                                                   ______________________________________                                    

As can be seen from Tables 1-4, the compositions of the presentinvention to which components (a), (b), (c), and (d) are incorporatedexhibited excellent intake valve detergency effects.

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims, theinvention may be practiced other than as specifically described herein.

What is claimed is:
 1. A gasoline composition comprising,(a) gasoline,(b) 1-10,000 ppm of a deposit inhibitor or a detergent containing abasic nitrogen atom, (c) 1-10,000 ppm of a carrier oil, and (d) 1-5,000ppm of an ester of a fatty acid and an alkylene oxide addition compound,wherein the compound to which the alkylene oxide is added has thefollowing formula (1), ##STR13## wherein X represents ##STR14## whereinZ¹ and Z² are individually a hydrogen atom, a trifluoromethyl group, ora substituted or unsubstituted alkyl or alkenyl group having 1-6 carbonatoms, or a phenyl group, and Y¹ and Y² are individually a hydrogen atomor a substituted or unsubstituted alkyl or alkenyl group having 1-6carbon atoms, or a phenyl group.
 2. The gasoline composition accordingto claim 1, wherein the component (b) is a compound selected from thegroup consisting of polyether amine compounds, long-chain alkylaminecompounds, long-chain alkenylamine compounds, benzylamine compounds, andsuccinimide compounds.
 3. The gasoline composition according to claim 1,wherein the component (b) is a compound selected from the groupconsisting of polyether amine compounds, long-chain alkylaminecompounds, and long-chain alkenylamine compounds.
 4. The gasolinecomposition according to claim 1, wherein the component (b) is apolyether amine compound.
 5. The gasoline composition according to claim1, wherein the component (b) is a polyether compound represented byformula (2-a).
 6. The gasoline composition according to claim 1, whereinthe component (c) is an alkylene oxide adduct to an alcohol or analkylphenol containing 10-50 carbon atoms.
 7. The gasoline compositionaccording to claim 1, wherein the component (d) further comprises acompound obtained by the ester exchange reaction of an alcohol and atriglyceride fat or oil or an alkylene oxide adduct thereof.
 8. Thegasoline composition according to claim 1, wherein the component (d-1)is a fatty acid ester of alkylene oxide adduct to bisphenol A.
 9. Thegasoline composition according to claim 1, wherein the component (b) isa compound selected from the group consisting of polyether aminecompounds, long-chain alkylamine compounds, and long-chain alkenylaminecompounds, and the component (c) is an alkylene oxide adduct to analcohol or an alkylphenol containing 10-50 carbon atoms.
 10. Thegasoline composition according to claim 1, wherein the component (b) isa compound selected from the group consisting of polyether amine-typecompounds, long-chain alkylamine compounds, and long-chain alkenylaminecompounds; the component (c) is an alkylene oxide adduct to an alcoholor an alkylphenol containing 10-50 carbon atoms; and the component (d)further comprises a compound obtained by the ester exchange reaction ofan alcohol and a triglyceride fat or oil or an alkylene oxide adductthereof.
 11. The gasoline composition according to claim 1, wherein theratio by weight of the component (b) to the component (d) is(b):(d)=99.5:0.5 to 70:30.
 12. A gasoline composition comprising,(a)gasoline, (b) 1-10,000 ppm of a deposit inhibitor or a detergentcontaining a basic nitrogen atom, (c) 1-10,000 ppm of a carrier oil, and(d) 1-5,000 ppm of an ester of a fatty acid and an alkylene oxideaddition compound, wherein the compound to which the alkylene oxide isadded has the following formula (a), ##STR15## wherein X represents##STR16## and Z² are individually a hydrogen atom, a trifluoromethylgroup, or a substituted or unsubstituted alkyl or alkenyl group having1-6 carbon atoms, or a phenyl group, and Y¹ and Y² are individually ahydrogen atom or a substituted or unsubstituted alkyl or alkenyl grouphaving 1-6 carbon atoms, or a phenyl group.